Solar thermal aerogel receiver and materials therefor

ABSTRACT

A silica aerogel having a mean pore size less than 5 nm with a standard deviation of 3 nm. The silica aerogel may have greater than 95% solar-weighted transmittance at a thickness of 8 mm for wavelengths in the range of 250 nm to 2500 nm, and a 400° C. black-body weighted specific extinction coefficient of greater than 8 m 2 /kg for wavelengths of 1.5 μm to 15 μm. Silica aerogel synthesis methods are described. A solar thermal aerogel receiver (STAR) may include an opaque frame defining an opening, an aerogel layer disposed in the opaque frame, with at least a portion of the aerogel layer being proximate the opening, and a heat transfer fluid pipe in thermal contact with and proximate the aerogel layer. A concentrating solar energy system may include a STAR and at least one reflector to direct sunlight to an opening in the STAR.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a divisional of application Ser. No. 16/079,172filed on Aug. 23, 2018 which is the national stage of International(PCT) Patent Application No. PCT/2017/019415, entitled “Solar ThermalAerogel Receiver and Materials Therefor” and filed on Feb. 24, 2017,which claims priority to and the benefit of U.S. Provisional PatentApplication No. 62/299,090, entitled “Solar Thermal Aerogel Receiver(STAR)” and filed Feb. 24, 2016, the entire contents of each of whichare incorporated by reference herein.

GOVERNMENT LICENSE RIGHTS

This invention was made with Government support under Grant No.DE-AR0000471 awarded by the Department of Energy. The Government hascertain rights in the invention.

FIELD OF THE INVENTION

In general, embodiments of the present invention relate to silicaaerogel materials and methods of fabrication, solar thermal aerogelreceivers, and solar energy systems.

BACKGROUND

Currently available solar energy systems, such as parabolic troughcollectors (PTCs), suffer from high cost per unit of exergy. Moreover,commercially available aerogels do not have the material propertiesnecessary for use in a high-efficiency solar thermal receiver for usewith e.g., flat reflectors. For example, currently available aerogelsare typically not suitable for use at the high operating temperaturesthat facilitate efficiency.

SUMMARY

In accordance with embodiments of the invention, a high-performanceair-stable solar thermal receiver includes a hot thermal absorberinsulated by an optically transparent thermal insulator, referred toherein as the solar thermal aerogel receiver (STAR). The innovativestack includes a monolithic aerogel layer that is optically transparentand thermally insulating (OTTI) and a black absorber in which theworking fluid may be heated. The receiver may have the ability toachieve maximum solar-to-exergy conversion efficiencies of >37% at anoptical concentration of 40 suns, providing thermal energy from thethermal absorber, at a reduced total system cost per unit exergy of<1/Wx, and an estimated lifetime of >25 years.

The technology described herein, including the optically transparent andthermally insulating aerogels, may be useful for concentrating solarpower (CSP), as well as solar heating and cooling applications. CSP isan especially promising technology for solar thermal conversion.(Weinstein, L. A., et al., Chem. Rev. 2015, 115, 12797-12838).

In an aspect, embodiments of the invention relate to an aerogel materialincluding silica aerogel defining a porous material with pores having amean radius of less than 5 nm with a standard deviation of 3 nm.

One or more of the following features may be included. The aerogelmaterial may include percent solids of less than 10%. The aerogelmaterial may include a mean particle size of 1.3 nm. The silica aerogelmay have a solar absorptance of >0.9 and IR emittance of <0.3 when inthermal contact with a black absorber at a temperature of 400° C.

The description of elements of the embodiments of other aspects of theinvention may be applied to this aspect of the invention as well.

In another aspect, embodiments of the invention relate to an aerogelmaterial including silica aerogel having (i) greater than 95%solar-weighted transmittance at a thickness of 8 mm for wavelengthsselected from the range of 250 nm to 2500 nm; and (ii) a 400° C.black-body weighted specific extinction coefficient of greater than 8m²/kg for wavelengths selected from the range of 1.5 μm to 15 μm.

One or more of the following features may be included. The silicaaerogel may have a thermal conductivity of less than 0.025 W/mK at roomtemperature and less than 0.1 W/mK at 400° C.

The description of elements of the embodiments of other aspects of theinvention may be applied to this aspect of the invention as well.

In another aspect, embodiments of the invention relate to a method forforming a silica aerogel. The method may include the steps of dilutingtetramethyl orthosilicate (TMOS) by methanol to create a TMOS solution;and adding an ammonia solution comprising ammonia and water to the TMOSsolution to form a silica aerogel precursor. The molar ratio of ammoniato TMOS may be less than 0.0025.

One or more of the following features may be included. The method mayfurther include allowing the silica aerogel precursor to gel, therebyforming the silica aerogel. The method may further include annealing thesilica aerogel to reduce the size of pores in the silica aerogel. Thepores may have a mean radius of less than 5 nm with a standard deviationof 3 nm. This pore size may be attained either before or afterannealing.

The method may further include increasing the spectral selectivity ofthe aerogel insulation layer may by doping the silica aerogel withnanoparticles, such as tin oxide, indium tin oxide, carbon etc., thathave strong absorption in the mid-infrared range.

The description of elements of the embodiments of other aspects of theinvention may be applied to this aspect of the invention as well.

In another aspect, embodiments of the invention relate to a solarthermal aerogel receiver which may include (i) an opaque frame definingan opening; (ii) an aerogel layer disposed in the opaque frame, with atleast a portion of the aerogel layer being disposed proximate theopening; and (iii) a heat transfer fluid pipe in thermal contact withand proximate the aerogel layer.

One or more of the following features may be included. The aerogel layermay include silica aerogel. The silica aerogel may define a porousmaterial with pores having a mean radius of less than 5 nm with astandard deviation of 3 nm. The aerogel layer may include an absorberlayer. The aerogel layer may include silica aerogel having (i) greaterthan 95% solar-weighted transmittance at a thickness of 8 mm forwavelengths selected from the range of 250 nm to 2500 nm; and (ii) a400° C. black-body weighted specific extinction coefficient of greaterthan 8 m²/kg for wavelengths selected from the range of 1.5 μm to 15 μm.

The heat transfer fluid pipe may include a black absorber layer.

The solar thermal aerogel receiver may further include a transparentouter layer disposed in the opening in the opaque frame. The transparentouter layer may include at least one of glass and a transparent polymer.The transparent outer layer may form at least a portion of a flat bottomsurface of the opaque frame. The aerogel layer may be in direct contactwith the transparent outer layer. The transparent outer layer and theaerogel layer may define an air gap therebetween. The opaque frame mayfurther include an insulating layer.

The receiver may have a maximum solar-to-exergy conversion efficiency ofgreater than 35% at an optical concentration of 40 suns.

The description of elements of the embodiments of other aspects of theinvention may be applied to this aspect of the invention as well.

In another aspect, embodiments of the invention relate to aconcentrating solar energy system including a solar thermal aerogelreceiver and at least one reflector configured to direct sunlight to theopening. The solar thermal aerogel receiver may include an opaque framedefining an opening, an aerogel layer disposed in the opaque frame, withat least a portion of the aerogel layer being disposed proximate theopening, and a heat transfer fluid pipe in thermal contact with andproximate to the aerogel layer.

One or more of the following features may be included. The aerogel layermay include an absorber layer. The aerogel layer may include silicaaerogel. The silica aerogel may define a porous material with poreshaving a mean radius of less than 5 nm with a standard deviation of 3nm. The aerogel layer may include silica aerogel having (i) greater than95% solar-weighted transmittance at a thickness of 8 mm for wavelengthsselected from the range of 250 nm to 2500 nm; and (ii) a 400° C.black-body weighted specific extinction coefficient of greater than 8m²/kg for wavelengths selected from the range of 1.5 μm to 15 μm.

The heat transfer fluid pipe may include a black absorber layer. Theopaque frame may further include an insulating layer. The solar thermalaerogel receiver may have a maximum solar-to-exergy conversionefficiency of greater than 35% at an optical concentration of 40 suns.

The concentrating solar energy system may further include a transparentouter layer disposed in the opening. The transparent outer layer mayinclude at least one of glass and a transparent polymer. The aerogellayer is in direct contact with the transparent outer layer. Thetransparent outer layer and the aerogel layer may define an air gaptherebetween.

The transparent outer layer may form at least a portion of a flat bottomsurface of the opaque frame. The description of elements of theembodiments of other aspects of the invention may be applied to thisaspect of the invention as well.

BRIEF DESCRIPTION OF THE DRAWINGS

In the drawings, like reference characters generally refer to the sameparts throughout different views. Also, the drawings are not necessarilyto scale, emphasis instead generally being placed upon illustrating theprinciples of the invention. In the following description, variousembodiments of the invention are described with reference to thefollowing drawings, in which:

FIG. 1A is a flow chart of a sol-gel process in accordance with anembodiment of the invention;

FIGS. 1B-1E are chemical diagrams illustrating silica aerogelfabrication in accordance with embodiments of the invention;

FIG. 2 is a graph comparing spectral transmittance of silica aerogel inaccordance with an embodiment of the invention to glass and commerciallyavailable silica aerogel;

FIGS. 3A-3B are graphs comparing the pore size of a commerciallyavailable aerogel with a silica aerogel in accordance with an embodimentof the invention;

FIG. 4 is a graph of the pore radius in a silica aerogel in accordancewith an embodiment of the invention;

FIGS. 5A-5C are graphs of the transmittance of silica aerogels and theirabsorption and scattering coefficients in accordance with an embodimentof the invention;

FIGS. 6A-6B are a photograph and micrograph, respectively, of silicaaerogels in accordance with embodiments of the invention;

FIG. 7 is a graph of the transmittance through silica aerogel as afunction of sample thickness;

FIG. 8 is a silica aerogel specific extinction coefficient measured andreported in the literature (U. Heinemann, R. Caps, and J. Fricke,International Journal of Heat and Mass Transfer 39 (10), 2115 (1996));

FIGS. 9A-9B are illustrations of a STAR receiver and a concentratingsolar energy system in accordance with an embodiment of the invention;

FIGS. 10A-10B are graphs of the temperature profile within the OTTIaerogel layer and the receiver efficiency in accordance with embodimentsof the invention;

FIG. 11 is a schematic showing the different components of a STARreceiver in accordance with an embodiment of the invention;

FIGS. 12A-12E are illustrations of an assembly process for a STARreceiver, in accordance with embodiments of the invention;

FIGS. 13A-13C are schematic illustrations of the STAR receiver inaccordance with alternative embodiments of the invention;

FIGS. 14A-14D are illustrations of different receiver configurations ofthe STAR system in accordance with embodiments of the invention;

FIG. 15 is a CAD model of a layout of the STAR receiver in accordancewith an embodiment of the invention;

FIG. 16 is a piping and instrumentation diagram for the STAR receiver inaccordance with an embodiment of the invention;

FIG. 17 is a photograph of an on-sun test prototype of an embodiment ofthe STAR receiver; and

FIG. 18 is a graph comparing the stagnation temperatures of anaerogel-insulated solar absorber in accordance with embodiments of theinvention to a bare absorber.

DETAILED DESCRIPTION

The STAR configuration provides high receiver efficiency at low cost.The performance enhancement may be achieved through the reduction ofthermal losses due to aerogel properties and receiver design. Costreduction may be at least partially attributed to the STAR being wellsuited for use with linear Fresnel reflector (LFR) concentrating optics,which may be significantly cheaper than the commonly used parabolictrough concentrators (PTC). The STAR receiver may include air stableabsorber coatings/aerogels that further eliminate the cost andcomplexity of a vacuum-evacuated receiver, which is the industrystandard. The inclusion of air-stable absorber coatings/aerogels alsoenables operation at higher temperatures (up to 600° C.), which furtherincreases receiver efficiency.

Silica Aerogel Properties

In some embodiments of the invention, a silica aerogel is synthesizedwith improved material properties, allowing the silica aerogel to, e.g.,enhance the performance of the STAR. Silica aerogels have a spectralselectivity that allows solar radiation to pass through the bulk yettrap infrared (IR) radiation. In this way, silica aerogels may be bothoptically transparent and thermally insulating.

Generally, the thermal insulation characteristics of aerogelseffectively reduce the outer surface temperature, reducing the overallheat loss in the STAR compared to the overall heat loss in vacuum-gapreceivers. Silica aerogels may increase receiver efficiency and reducedconcentration requirements. Aerogels are transmissive at most solarwavelengths because there are no absorption modes for silica at thesewavelengths. However, Rayleigh scattering, which is a function ofaerogel pore size, reduces the transmission for short wavelengths. Byvarying the pH during the aerogel synthesis process, and/or varying thedrying time during the drying process, the pore size and Rayleighscattering may be controlled. Although silica aerogels are naturallystrongly absorbing from 5-30 μm, absorption from 3-5 μm may be increasedthrough the addition of water or other dopants into the aerogel asfurther described below.

The thermal conductivity of an aerogel also depends strongly on theaerogel microstructure, which is improved in conjunction with tailoringof optical properties. The thickness of the aerogel also affects theproperties of the aerogel, whereby thicker aerogels reduce the surfacetemperature and corresponding radiative and conductive losses. However,a thicker aerogel may also result in a decrease of the opticaltransmission. The optimal thickness is therefore that which maximizesthe exergetic efficiency of the system. In some embodiments, an 8 mmaerogel sample has a thermal conductivity of less than 0.025 W/mK atroom temperature and less than 0.1 W/mK at 400° C. By reducing thethermal losses from the system, aerogels also reduce the amount ofoptical concentration required for a desired thermal efficiency.

Silica Aerogel Fabrication Process

The synthesis of a silica aerogel is described herein. The synthesizedsilica aerogel may have properties suitable for use in an embodiment ofthe STAR. In general, several synthesis variables (e.g., chemical ratio,aging period, aging temperature and drying conditions) affect thespectral selectivity, thermal, and structural properties of aerogels.The absorption of radiation in an aerogel is proportional to itsdensity. The scattering of radiation is a function of the particle sizeand pore size within the aerogel, which is not only a function ofdensity, but also of the aerogel synthesis technique. By adjusting thepH of the sol-gel solution, the particle and mesoporous structure ofaerogels can be tuned, thus changing the scattering coefficient. Afurther increase in spectral selectivity of the aerogel insulation layermay be achieved by doping aerogels with nanoparticles, such as tinoxide, indium tin oxide, carbon etc., that have strong absorption in themid-infrared range.

The synthetic method for creating an embodiment of the silica aerogeldescribed herein is based on Tamon et al.'s (hereafter referred to asTamon) recipe for silica aerogel using tetramethyl orthosilicate (TMOS)as silica precursor and ammonia (NH₃) as catalyst. See H. Tamon, T.Sone, and M. Okazaki, Journal of Colloid and Interface Science 188 (1),162-167 (1997), the entire contents of which are incorporated byreference herein. Unlike Tamon's method where NH₃ is mixed with TMOSsolution before adding H₂O, methods disclosed herein combine NH₃ withH₂O first, and then add the NH₃ solution to the TMOS solution.

To synthesize silica aerogel, sol-gel polymerization may be used asdepicted in FIG. 1A. In a process in accordance with an embodiment ofthe invention, TMOS is diluted in methanol to create a TMOS solution100. The TMOS solution 100 is then mixed at room temperature with asolution of NH₃ and H₂O 102 (step 104). In this step, TMOS 106 undergoeshydrolysis via the chemical process shown in FIG. 1B, where one of themethyl groups 108 of the TMOS 106 is replaced with a hydrogen, releasingmethanol 110 in the process. After the sol is created through the mixingprocess 104, it is placed in a container of the desired shape andallowed to gel for e.g., two weeks 112. After two weeks, ethanol (EtOH)is added to the wet-gel in preparation for critical point drying (CPD)114. EtOH is used as it is miscible with liquid carbon dioxide (CO₂). Toprevent the formation of cracks, the wet-gel may be dried slowly tominimize capillary pressure during the CPD process 116. CPD may includecooling, introduction of liquid CO₂, pressurization, anddepressurization. During depressurization at the end of CPD, a 100psi/hr bleeding rate may be used to decrease the CPD chamber pressurefrom e.g., ˜4300 psi to ambient pressure. The final structure of thesilica aerogel 118 is shown in FIG. 1E.

In some embodiments, the aerogel may be made water-repellant by treatingwith a hydrophobic reagent. As before, the aged gel may be removed fromthe mold and transferred into a glass container with pure EtOH. Thehydrophobic reagent (e.g., hexamethyldisilazane ((CH₃)₃Si)₂NH) may beadded in the ethanol, at a ratio to the ethanol of, e.g., 1:9. The agedgel may be then kept in the solution at room temperature and dried inCPD as described before.

In some embodiments, the high-temperature stability of the aerogel isimproved by providing coating having a thickness of a few nanometers(e.g., <5 nm) to the aerogel. This coating may be formed by atomic layerdeposition of Al₂O₃ or HfO₂. This allows the aerogel to maintainstructural robustness even at temperatures >600° C., without sacrificingthe optical transparency and thermal insulating properties.

This method, in which NH₃ is combined with H₂O first and then added tothe TMOS solution, promotes the protonation of NH₃ in H₂O resulting insufficient hydroxide ion (—OH) in the solution. The amount of —OHsignificantly affects the rate of hydrolysis and condensation reactions(FIGS. 1B-1D), which dictate the particle size and pore size of silicaaerogel. Additionally, Tamon reports a mixing mole ratio of [NH₃]:[TMOS]of 0.0737 yielding an aerogel with a pore radius of 6 nm and atransmission of 84% at a 600 nm wavelength. To obtain a mean pore radiusof 5 nm or less, a molar mixing ratio of NH₃:TMOS:water:methanol of0.0025:1:4:6 may be used, with the ratio of NH₃ to TMOS being 0.0025 orless. For example, in one embodiment, a molar mixing ratio ofNH₃:TMOS:water:methanol equal to 0.0019:1:4:6 yields a silica aerogelwith a pore radius of 2.3 nm. This embodiment demonstrates a solarweighted transmittance of 96% at 8 mm sample thickness. Accordingly, apreferred molar ratio of NH3 to TMOS to achieve the desired pore size toachieve sufficiently high optical transparency is 0.0019±0.0005. Someembodiments demonstrated 95% transmittance at a 600 nm wavelength asshown in the graph depicted in FIG. 2.

The synthesis chemistry, pH and drying dynamics may be tuned to obtainOTTI layers with properties that allow for both low thermal conductivity(<0.025 W/mK at room temperature) and high transmissivity in the250-1100 nm wavelength range for solar radiation.

Table 1 shows the properties of an un-annealed OTTI silica aerogel inaccordance with an embodiment of the invention, compared with theproperties of a commercially available aerogel as measured using SmallAngle X-ray Scattering (SAXS).

TABLE 1 Commercial aerogel OTTI aerogel sample (un-annealed) NominalParticle Size 1.29 ± 0.05 nm 1.12 ± 0.06 nm Nominal Pore Size 10.25 ±0.03 nm  5.86 ± 0.03 nm Pore Standard Deviation — 3.1 nm Mean scatteringradius 4.16 ± 0.01 nm 2.92 ± 0.01 nm

These measurements indicate smaller particle size and pore size of thesynthesized OTTI silica aerogel than the commercially available aerogel.The smaller particle and pore size are advantageous in giving the OTTIsilica aerogel the properties that enable it to be used in the STARreceiver.

Aerogel Property Enhancement using Annealing

FIG. 3A is a graph of un-annealed aerogel pore size distribution(measured using SAXS). The graph shows the pore radius of the OTTIsilica aerogel and of a commercially available silica aerogel monolith.The embodiment of an OTTI aerogel shown in FIG. 3A has a smaller poreradius over a narrower distribution than a commercially availableaerogel. FIG. 3B shows the raw SAXS measurement data showing thescattering intensity as a function of the scattering vector. In FIG. 3B,Q is the scattering vector, where Q is inversely proportional to thesize of the aerogel features. Thus, the exemplary OTTI silica aerogeldemonstrates a greater number of small features (e.g., pores) than thecommercially available aerogel.

FIG. 4 shows the OTTI silica aerogel pore size distribution as measuredby SAXS and by Brunauer-Emmett-Teller analysis (BET) for an embodimentof an un-annealed OTTI aerogel. It is known by one of skill in the artthat SAXS and BET yield slightly different measurements because theyemploy different methodologies. Nevertheless, both measurements of thepore size of the un-annealed aerogel show a peak in the distribution ofa pore size of less than 5 nm.

High temperature annealing of the above described silica aerogel mayeliminate hydrophilic groups (—OH) on the surface of aerogel resultingin enhancement of transmission in the absorption region (>1100 nm) byminimizing molecular absorption. Some embodiments of OTTI silicaaerogels demonstrate suitable thermal stability at 400° C., whichcorresponds to the 391° C. maximum outlet temperature of the STARreceiver. Annealing may take place in an oven at a temperature of 400°C., reached by increasing the oven temperature by 10° C./min. Forexample, a 1200° C. dual split tube furnace, OTF-1200X, available fromMTI Corporation may be used. In some embodiments, the aerogel isannealed for 336 hours. After annealing, the aerogel sample may becooled in a ceramic dish.

For one embodiment, a durability test was conducted where the aerogelsample was annealed in an oven at high temperature for a long durationand allowed to rest at ambient conditions. For example, FIG. 5A showsthe spectral transmission of a 4 mm thick aerogel sample annealed at400° C. for 336 hours and rested for 552 hours 520 indicating anenhancement of transmittance in the solar spectrum (250-2500 nm) and theinfrared spectrum of interest (>2500 nm). FIG. 5A compares thetransmittance of this aerogel sample fabricated using the TMOS precursorbefore annealing at high temperature 524, after annealing 522, and afterresting at ambient temperature 520. FIG. 5A inset shows an image of anoptically transparent, thermally insulating monolithic silica aerogelsample. The data shows that while the maximum total transmission may bereached immediately after annealing, when the aerogel is allowed to restat room temperature, the optical properties partially rebound towardstheir initial state. By allowing the samples to rest for long periods oftime, a final rested state of material properties may be reached tocompare to the initial and annealed states. Examining aerogel samples atthese three stages allows the identification of properties that changeirreversibly and reversibly with annealing, and the corresponding timescales, such as transmission, absorption, etc.

FIG. 5B shows the absorption coefficient, σ_(a), corresponding to FIG.5A which is the dominant mode of transmission loss at wavelengths >1000nm of the silica aerogel before annealing. The data shows that theabsorption coefficient may be changed over the wavelengths of interestby annealing. This change may be due to water adsorption within theinner surface of the material. Silica aerogels are naturally hydrophilicand can adsorb 5-15 wt % water in ambient conditions. Annealing theaerogel samples for a sufficiently long time and at high temperaturesmay drive out adsorbed water and decrease water absorption and overalldensity, resulting in higher transmission. The sample may readsorb waterwhen left at ambient conditions, thereby reducing the overalltransmittance. The readsorbed water may increase the mass of the restedaerogels and may cause the absorption coefficient to increase. However,irreversible change in the absorption coefficient is shown by thedifference between the original transmittance and the transmittance ofthe annealed rested samples. This difference in transmittance may becaused by a surface chemistry change during which hydrophilic —OH bondsundergo a condensation reaction and join together to release an H₂Omolecule, leaving behind a Si—O—Si surface bond and making the aerogelmore hydrophobic. The annealed and rested aerogels may have a decreasedaffinity for water absorption and may uptake less water after resting.The decrease in hydrophilicity may also increase the time needed tocompletely readsorb water, i.e., a sample annealed for a longer time maytake longer to reach a final rested state.

FIG. 5C shows the scattering coefficients, Gs, for the same aerogelsample before 524 and after 522 being annealed for 336 hours at 400° C.The scattering coefficient (FIG. 5C) may have a smaller absolute changein comparison to the absorption coefficient (FIG. 5B), but since thescattering coefficient is highest at wavelengths where the solarspectrum peaks, a decrease in the scattering coefficient is advantageousin achieving high solar transmission. During annealing, the supportingnetwork of the aerogel sample may experience structural relaxation andthermally-driven condensation. High temperature exposure may decreasethe viscosity of the silica particles and allow for the material tocontract and rearrange itself into a less energetic state, which maylead to a change in both particle and pore size of the network. A changein the particle and pore size may decrease the effective scattering sizeand increase the optical transmittance.

The optically transparent thermally insulating OTTI silica aerogellayers provide the desired optical transparency and thermal insulationfor use in solar thermal receivers. The OTTI layer serves to reduce theradiation, conduction, and convection heat losses from the hot absorberto the ambient. FIG. 6A is a photograph of a 7 cm diameter CPD driedsilica aerogel sample that has undergone annealing indicating theoptical transparency of the sample. FIG. 6B is a scanning electronmicroscope (SEM) image of fabricated silica aerogel that has not beenannealed with large surface area and high porosity. Some embodiments ofthe OTTI silica aerogel demonstrate 96% solar weighted transmittancethrough 8 mm thickness and a heat transfer coefficient <7 W/m²K between400° C. and 100° C. In some embodiments, these properties may beretained even after subjecting aerogel samples to high temperatures(e.g., 400° C.) and high humidity (e.g., >80% RH) conditions for >100hours.

Table 2 summarizes monolithic silica aerogel SAXS characterizationbefore and after annealing at 600° C. for 4 hours;

TABLE 2 Before Annealing After Annealing Solar-weighted transmittance95.6 ± 0.3%   98.0 ± 0.3%   (4 mm thick sample) Particle size 1.29 ±0.05 nm 1.30 ± 0.06 nm Pore size 4.70 ± 0.02 nm 4.28 ± 0.02 nm Meanscattering length 2.91 ± 0.03 nm 2.79 ± 0.02 nm

The data in Table 2 demonstrates the increase in solar-weightedtransmittance and decrease in pore size that may be achieved throughannealing of the silica aerogel.

In some embodiments, the mean pore radius of the silica aerogel is lessthan 5 nm with a standard deviation of 3 nm. In some embodiments thesilica aerogel has a mean particle size of 1.3 nm and includes solids ofless than 10%. In some embodiments, an 8 mm thick silica aerogel inthermal contact with a blackbody absorber has a solar absorptance ofgreater than 0.9 and an IR emittance of less than 0.3 at hightemperatures, such as ˜400° C.

Aerogel Optical Properties

In a preferred embodiment, total transmission of the OTTI aerogel isincreased while still maintaining good physical stability. Commerciallyavailable monolithic OTTI aerogels (e.g., Aerogel Technologies™)demonstrate transmission of ˜85%. In some embodiments, the STAR receiverrequires higher transmission (e.g., >95% transmission) than thetransmission achieved with commercially available aerogels. Hightransmission may be achieved in the silica aerogel by controlling thepore size and silica particle size of the aerogel, i.e., small pore andparticle sizes with narrow distributions increase transmission, throughthe above described synthesis method and annealing process.

OTTI aerogels demonstrate suitable spectral properties for use withembodiments of the STAR. OTTI aerogels demonstrate 96% solar-weightedtransmittance over a 250-2500 nm wavelength through an 8 mm thicksample, as indicated in FIG. 2, i.e., a graph of the comparison oftransmittance of glass, a commercially available aerogel, and anembodiment of the silica aerogel used in the STAR measured with aUV-Vis-NIR spectrophotometer using an integrating sphere. In someembodiments, the silica aerogel has greater than 95% solar-weightedtransmittance at a thickness of 8 mm for wavelengths selected from therange of 250 nm to 2500 nm. In general, the high porosity of aerogels(>90%) cause them to have a refractive index ˜1, which minimizesreflection losses. Some embodiments of the OTTI aerogels alsodemonstrated suitable thermal stability at 400° C., which corresponds tothe 391° C. maximum outlet temperature of the STAR receiver.

FIG. 7 shows solar weighted transmittance as a function aerogelthickness in mm. The lines are model results for thicknesses forscattering diameters, d_(s)=3, 6, 12 nm (corresponding to scatteringradii of 1.5, 3, 6 nm respectively) and the dots are measurements from asilica aerogel sample. The filled dots represent measurements on asingle sample. The open dots represent measurements of a stack of twosamples. The additional interface introduced by stacking two samplesdoes not introduce noticeable deviation from the model because of theaerogel's refractive index of ˜1. The dashed line shows the solartransmittance of soda lime glass as a reference. In this embodiment, theaerogel demonstrates increased solar transmittance over soda lime glassin agreement with that predicted by the model for a scattering diameterof 6 nm (equivalent to scattering radius of 3 nm).

Aerogel Thermal Properties

Generally, two properties determine how effective an aerogel is as aninsulator: the spectral extinction coefficient and the thermalconductivity including solid conduction and gaseous conduction. Thespectral extinction coefficient may be measured using Fourier transforminfrared spectroscopy (FTIR). While it is difficult to measure the solidthermal conductivity directly because radiation cannot be eliminated, ifthe radiative properties of the aerogel are known, the thermalconductivity can be deduced from aerogel conductance measurements.

A detailed numerical model of the radiative transfer within an aerogelmay be used to tune an OTTI layer for a given incident spectrum,operating temperature, and ambient conditions. A model may be used tosolve the spectral equation of radiative transfer and couple it to theheat equation. The radiative transfer equation (Equation 1) and the heatequation (Equation 2) are shown below:

$\begin{matrix}{\frac{{dI}_{\lambda}(\Omega)}{dx} = {{{- K_{e_{\lambda}}}{I_{\lambda}(\Omega)}} + {K_{a_{\lambda}}I_{b\; \lambda}} + {\frac{K_{s_{\lambda}}}{4\pi}{\int\limits_{0}^{4\pi}{{I_{\lambda}\left( \Omega^{\prime} \right)}{p_{\lambda}\left( \Omega^{\prime}\rightarrow\Omega \right)}d\; \Omega^{\prime}}}}}} & (1) \\{{\frac{d}{dx}\left( {{k\frac{dT}{dx}} - q_{R}} \right)} = 0} & (2)\end{matrix}$

where K_(eλ) is the spectral extinction coefficient, K_(sλ) is thescattering coefficient, K_(aλ) is the absorption coefficient, I_(λ) isthe spectral intensity, I_(bλ) is the spectral blackbody intensity,p_(λ) is the scattering phase function, Ω is the solid angle, x is theposition in the sample, T is the temperature, k is the thermalconductivity, and q_(R) is the radiative heat flux. The radiative heatflux is given below:

$\begin{matrix}{q_{R} = {\int\limits_{0}^{\infty}{\int\limits_{4\pi}{{I_{\lambda}(\Omega)}d\; \Omega \; d\; \lambda}}}} & (3)\end{matrix}$

The model may use the spectral extinction coefficient (K_(eλ)), which isthe sum of the scattering (K_(sλ)) and absorption coefficients (K_(aλ)),as an input to solve the radiative transfer equation.

FIG. 8 shows the measured specific spectral extinction coefficient of anun-annealed embodiment of the silica aerogel used in the STAR receiver.Also shown in FIG. 8 are the extinction coefficients from the literatureand the blackbody spectrum at 400° C. (black dashed line) for reference.In some embodiments, the measured extinction coefficient for the silicaaerogel is higher than the literature data, particularly in the 3-5 μmwavelength region. The higher extinction coefficient may be attributedto absorption due to water molecules “bonded” to the aerogel surface.Larger extinction of the silica aerogel may advantageously translate tobetter insulation at high temperatures around 400° C.

The typical aerogel 400° C. black-body weighted specific extinctioncoefficient may be measured to be around 10±0.5 m²/kg, based on IRtransmittance measurements (shown in FIG. 8). In some embodiments, the400° C. black-body weighted specific extinction coefficient is greaterthan 8 m²/kg for wavelengths selected from the range of 1.5 μm to 15 μm.The relatively high value of the specific extinction coefficientindicates the effectiveness of the OTTI aerogel to suppress thermalradiation at high temperatures around 400° C.

The radiative transfer equation (RTE) model, described previously,predicts heat transfer coefficients of <7 W/m²K at the operatingtemperatures of the STAR receiver (e.g., T_(High)=400° C. andT_(Low)=100° C.). Low values of heat transfer coefficients represent aninsulator at the high operating temperatures of the STAR receiver.

Receiver Design and Performance

Referring to FIG. 9A, a concentrating solar energy system 926 includes asolar thermal aerogel receiver (STAR) 928 and an array of reflectors 930configured to direct sunlight to the STAR 928. Referring also to FIG.9B, the STAR 928 includes an opaque frame 932 defining an opening 934.The frame is preferably made from a rigid material, such as stainlesssteel. A transparent outer layer 936 may be disposed in the opening 934and is preferably formed from a transparent, rigid material such asglass, and defines at least a portion of a flat bottom surface of theframe 932. In some embodiments, the transparent layer 936 may be formedof a robust, transparent polymer, e.g., fluorinated ethylene propylene(FEP). The use of a polymer may be advantageous by minimizing theoptical losses (due to its low refractive index compared to glass), aswell as reducing the cost and weight of the receiver. A layer includingaerogel 938, such as the OTTI silica aerogel described above, isdisposed in the frame 932, with at least a portion of the aerogel layerbeing proximate the opening in the frame. In some embodiments, as longas the aerogel layer is sufficiently supported in the frame, notransparent outer layer needs to be included in the opening, therebyfurther reducing costs. In other embodiments, the transparent outerlayer 936 may be provided to help support and protect the aerogel layer.

The layer of aerogel 938 is in thermal contact with and proximate to oneor more heat transfer fluid pipes 940 housed in the frame 932. Theabsence of a gap or vacuum between the aerogel layer and the heattransfer fluid pipes, as is present in currently available receivers,reduces heat loss due to conduction and convection and reduces thereceiver height. A reduction in receiver height may increase the amountof incident light that travels through the aerogel layer and reaches theheat transfer fluid pipes. The number of heat transfer fluid pipesdepends on the desired capacity of the receiver. In some embodiments, asillustrated, the receiver 928 contains six heat transfer fluid pipes.One or more of the heat transfer fluid pipes 940 may include a blackabsorber layer, e.g., black paint, to increase absorption.

A black absorber layer 942 may be disposed on the aerogel layer 938and/or on the one or more heat transfer fluid pipes 940. The blackabsorber layer 942 may be formed from a black material, e.g., stainlesssteel coated with black paint.

In some instances, the aerogel 938 defines an air gap between theaerogel 938 and the transparent outer layer 936 to prevent condensationon the interior of the transparent outer layer that may accumulate fromwater in the aerogel at high temperatures. In other embodiments, theaerogel layer 938 is disposed in the frame 932 in direct contact withthe transparent outer layer 936. In this embodiment, the transparentouter layer 936 provides mechanical stability to the aerogel layer 938.An additional advantage may be increased heat transfer between thetransparent outer layer 936 and the aerogel layer 938.

An insulating layer 944 may be disposed in the frame 932, e.g., abovethe pipes 940 and/or adjacent to the aerogel 938 in the portion of theframe 932 that is not optically active. The insulating layer 944increases the efficiency of the receiver 928 by preventing heat loss.

In some instances, the pipe or pipes 940 may be configured to relay aheat transfer fluid to a heat storage unit 946 from which heat may bedispatched.

In one embodiment, the STAR 928 is coupled with at least one reflector,e.g., a reflector array 930, such as an LFR to form the concentratedsolar energy system. The one or more reflectors may be configured todirect sunlight to the opening 934. The flat geometry, i.e., flat bottomsurface 936, of the receiver 928 makes it compatible with an LFR andhelps reduce IR losses.

The receiver 928 may be sized according to the width of the absorberlayer or number of heat transfer fluid pipes, such that at least 90% ofthe incident light from the reflector hits the absorber or heat transferfluid pipes. The height of the receiver may vary with the amount ofinsulation and the length may vary depending on the receiver's intendeduse, e.g., from 100 cm to 1000 m. For example, the frame 932 may be 10cm×30 cm×500 cm.

A thickness of the aerogel may be selected from a range of 5 mm to 15mm, depending on the aerogel properties and solar concentration.Referring also to FIG. 7, if the aerogel layer 938 is too thick, thetransmittance may be too low for the intended application. If theaerogel layer 938 is too thin, then it might result in excessive heatloss from the bottom surface. A thickness of the transparent outer layer936 may be selected from the range of 1 mm to 3 mm. The transparentouter layer is preferably thick enough that it is not prone to breaking,but not so thick that optical losses occur. An additional advantage of athinner transparent layer is that it reduces the overall cost of thereceiver.

Referring also to FIG. 9B, the receiver 928 may generate and captureheat as follows. Light from the sun may be reflected off the reflectorarray 930 towards the receiver 928 and transmitted through thetransparent outer layer 936. Some solar radiation may be reflected bythe transparent outer layer 936 and thereby may be lost to the ambient.Some heat may be released by the black absorber layer 942 and emitted asradiation. Some heat may also be lost by convection. The heat that istrapped by the black absorber 942 may be transferred through piping viaheat transfer fluid to the heat storage unit 946 to be used for e.g.,electricity generation or other industrial processes.

In some embodiments, the STAR receiver receives solar radiation from thereflector array at a concentration of about 40 suns. In some embodimentsof the STAR the transparent outer layer 936 defines a relatively wideaperture (e.g., 10-40 cm, compared to 7-9 cm for industry standardvacuum tubes). Additionally, in some embodiments, the receiver may befixed and supported more effectively to allow for a greater range ofoptimization in design geometry. The use of the previously describedsilica aerogel in the design allows for operating temperaturescomparable to conventional linear CSP receivers with less concentrationarea, meaning the footprint and supporting structures may be reducedwithout sacrificing efficiency.

The performance of an ideal blackbody absorber coupled with thepreviously described OTTI silica aerogel depends on several factorsincluding the operating temperature, aerogel thickness, and opticalconcentration. For example, for an 8 mm thick aerogel sample paired withan ideal blackbody absorber having an absorptance of 1 at 400° C., thesolar absorptance is 0.96 and the emittance in the IR is around 0.2.This expected performance relates to operation in air and is comparableto state-of-art high-temperature spectrally selective surfaces thatoperate in vacuum. In some embodiments, an 8 mm thick aerogel in thermalcontact with a blackbody absorber has a solar absorptance of greaterthan 0.9 and an IR emittance of less than 0.3 at high temperature suchas ˜400° C.

FIG. 10A shows a modeled temperature profile in the aerogel andtransparent outer layers of the STAR receiver. Thermal transport throughthe aerogel is modeled by coupling the equation of radiative transferand the heat equation in one dimension (through the thickness of theaerogel) as shown before. The temperature increases in the thickness ofthe aerogel layer closer to the absorber layer, which may have anoperating temperature of 391° C., while the surface of the transparentouter layer may be less than 150° C. The temperatures at 80 suns arehigher than the temperatures at 40 suns.

FIG. 10B is a graph of the STAR efficiency at concentrations of 40 and80 suns 1050, 1048. The dashed lines in FIG. 10B show the performance ofa state-of-the art spectrally selective (SS) surface for comparison.Efficiency increases with aerogel thickness up to about 5-10 mm(depending on the concentration) and the receiver efficiency at thatthickness is significantly higher than that of a spectrally selectivesurface, i.e., at least 0.85.

For a CSP system including the STAR, with properties of the synthesizedOTTI silica aerogel previously described, the model predicts a peakexergetic efficiency of 37.2% and an annual average exergetic efficiencyof 26.3%. Modeling may be used to identify the aerogel properties thatare required for improved system performance targets. For example, for a39.5% peak efficiency, the aerogel will need to be 98% transmitting andhave a heat transfer coefficient of 4 W/m²K through an 8 mm thickness.The estimated annual average exergetic efficiencies in this example areabove 31% with peak efficiencies exceeding 42% if the receiver isoperated at 500° C. Modeling of the heat transfer fluid (HTF)performance uses well established heat transfer correlations and fluidproperties known to one of skill in the art. Heat transfer within thesolid, non-aerogel portions of the receiver (i.e., pipe walls, absorberplates, insulation, etc.) may be modeled with Fourier's law.

Receiver Design and Fabrication

To decrease the total cost of the receiver, the assembly process may besimplified to use cost-effective components and processes. Referring toFIG. 11, the STAR receiver 1128 may have a frame 1132 formed from arelatively inexpensive material, such as aluminum or stainless steel.The transparent outer layer 1136, i.e., glass or transparent polymer, isdisposed in the collection window 1134 of the frame 1132. A layer ofaerogel 1138, such as the previously described OTTI silica aerogel, isdisposed in the collection window 1134, interior to the transparentouter layer 1136. The layer of aerogel 1138 is in thermal contact withone or more HTF pipes 1140, which may be coated with black paint 1152,such as Pyromark™ (LA-CO Industries Inc.). A layer of insulation 1144,such as Microsil microporous insulation (Zircar Ceramics, Inc.), isdisposed in the frame.

An exemplary process for fabricating an embodiment of a single modulesection of the STAR receiver is shown in FIGS. 12A-12E. First, analuminum U-channel frame 1232 is manufactured as a continuous piece viaan extrusion process. Next, the insulation 1244 is placed into thechannel in discrete blocks (bottom block and side blocks). The stainlesssteel pipes 1240, coated with Pyromark™ black paint, are laid into theopen cavity of the insulation 1244 and evenly spaced. The aerogel 1238and transparent outer layer 1236 are then laid on top of the pipes 1240,and a small piece of insulation is used to secure and center the glass.Two small aluminum strips 1254 a, 1254 b are then bonded to thetransparent outer layer 1236 (using a ceramic to metal bonding agent)and welded to the aluminum U-channel frame 1232. The receiver is thenrotated so that the U-channel is facing downward and the modules areready to be transported for installation.

A utility scale plant may include several 5 m long STAR modules joinedtogether. Two modules may meet at a fixed support where each module hasexposed HTF pipes. Bellows connectors may be welded to the pipes,allowing the modules to couple thermally. A custom made insulation piecemay be added around the bellows to prevent heat loss from the length ofreceiver that is not optically active (i.e., connection area between thetwo modules). Above the insulation piece an aluminum capping element maybe fixed to each module through a set of linear fasteners.

An alternative embodiment of the STAR receiver is shown in FIGS. 13A(perspective view) and 13B (bottom view). The receiver 1328 includes astainless steel sheet metal enclosure 1332 fabricated out of twoC-channels on the sides. The top cover and different receiver componentsat the bottom are bolted in place using C-channels with gaskets toprevent any water leakage into the receiver 1328. This embodiment of thereceiver 1328 includes a removable section that houses the OTTI aerogel1338 surrounded by rigid, non-transparent insulation 1344. The OTTIaerogel 1338 is protected by a transparent outer layer 1336. In thisembodiment, the OTTI aerogel 1338 does not sit directly on thetransparent outer layer 1336. Since the transparent outer layer 1336 isexposed to air and is lower in temperature than the aerogel 1338, thewater evaporated from the aerogel 1338 may condense on the transparentouter layer 1336 during heat up, and this may damage the aerogel 1338.This problem is avoided by suspending the aerogel 1338 on the edges suchthat an air gap is defined between the aerogel 1338 and transparentouter layer 1336. The exposed area of the transparent outer layer 1336is minimized by adding non-transparent thermal insulation 1344 a, 1344 bbelow it in the non-optically-active area of the receiver 1328. A thicknon-transparent insulation layer 1344 a, 1344 b is present below thetransparent outer layer 1336 on the side and another thin, rigidinsulation layer is added just below the transparent outer layer 1336 tominimize heat loss while preventing any optical interference to theconcentrated sunlight (incident from below). To further improveperformance, the non-transparent insulation on the sides of the aerogel1338 inside the cavity between the aerogel 1338 and pipe assembly 1340may be covered with specular, highly reflecting surfaces such as a goldleaf.

Referring to FIG. 13C, the STAR receiver 1328 has a removable section1356 that houses the aerogel 1338 in a rigid, opaque insulation 1344.This facilitates replacement of the aerogel.

Receiver Geometries

Different receiver configurations are illustrated in FIGS. 14A-14D.Referring to FIG. 14A, the HTF tubes 1440 may be directly coated withthe solar absorber 1452, and insulated with an aerogel layer 1438 on theilluminated side of the receiver 1428 and insulated with microporousceramic insulation 1444 on the other sides. Alternative embodiments ofthe STAR receiver may use an absorber plate 1442 rather than having thetubes 1440 absorb sunlight directly (FIG. 14B) or use vertical finsperpendicular to the pipes with an absorber coating connecting the tubes1440 (FIG. 14C).

A “vacuum tube” configuration is shown in FIG. 14D that uses a receiversimilar to a state of the art vacuum tube, but with an aerogel 1438 inplace of the vacuum tube. In this embodiment, an air-stable blackcoating 1458 is used rather than a spectrally selective coating. Thisembodiment of the STAR receiver may be suited for use with PTC, which istypically used with vacuum tubes, and may be less expensive and morerobust than existing vacuum tube receivers due to the lack of vacuum.Using the OTTI silica aerogel performance metrics mentioned above, theperformance may be slightly lower than current vacuum tubes (37.3% peakexergetic efficiency for this embodiment of the STAR receiver vs. 39.7%peak exergetic efficiency for the state-of-art in PTC). However, thisembodiment of the STAR receiver is not susceptible to loss of vacuum, aproblem for receivers using vacuum tubes (e.g., due to hydrogendecomposition of high temperature HTFs and subsequent permeation intothe vacuum gap).

Solar Thermal Receiver Assembly

An outdoor test system 1560 may be used to measure the performance ofvarious embodiments of the STAR receiver 1528. FIG. 15 provides a CADmodel of the outdoor test system 1560. The central STAR receiver 1528 iselevated and centrally located over a reflector array 1530. As shown bythe CAD model, the reflector array 1530 is symmetric about the receivercenterline. The reflectors are oversized to the south to minimizeoptical end effects associated with low solar elevation angles. Allpiping and process equipment (e.g., a storage tank 1562, an expansiontank 1564, a nitrogen tank 1566, etc.) is located on the north side ofthe reflector array 1530 to minimize shading during most solarpositions. The exemplary reflector array 1530 consists of ten mirrorassemblies 1568, each having a reflector element, a motor forsingle-axis tracking, and associated supporting brackets.

FIG. 16 is a piping and instrumentation diagram for the outdoor testsystem. A circulation pump 1670 circulates the HTF through the STARreceiver 1628 and the additional process equipment including anauxiliary heater 1672, flow meter 1674, chiller 1676 and instrumentationto measure the pressure and temperature at various points along the flowpath. The thermocouples 1678 closest to the receiver are used in theperformance characterization of the various embodiments of the STARreceiver 1628. These thermocouples 1678 are placed exactly at thereceiver HTF inlet and exit points. The bypass/recirculation line 1680allows for prototype setup, calibration, and testing operation withoutthe STAR receiver 1628 physically present. An expansion tank 1664 allowsfor HTF volume expansion due to change in temperature, and is mounted atthe highest point in the system. The drain back storage tank 1662 allowsthe entire volume of HTF to be drained by gravity at night time toprevent freezing of the HTF within the piping loop when the ambienttemperature drops below 12° C. The immersion heater 1682 then allows anysolidified HTF to be melted and heated to a pumpable temperature suchthat the system can be refilled through the expansion tank 1664 usingthe fill pump 1684. The nitrogen tank 1686 is connected to the expansiontank 1664 and serves the dual function of providing the requiredoverpressure to the system to prevent fluid boiling at elevatedtemperatures, and blanketing the HTF with an inert gas to prevent fluidoxidation and reduce fire hazards.

Standard piping and connections are used throughout to minimize set uptime. Since the physical system is symmetric about the receiver, forease of setup and wiring, the controls mimic the physical layout. Aprimary control cabinet (not shown) houses data acquisition (DAQ)components that are shared throughout the prototype (such as pump andcooler controllers and thermocouple board); while the auxiliary controlcabinets are used for motor controllers for the linear Fresnel reflectorelements.

Outdoor Prototype

FIG. 17 is a photograph of an embodiment of a concentrating solar energysystem 1726 that includes the demo STAR receiver 1728 during an on-suntest. On-sun testing of the demo may be used to determine the stagnationtemperature of an aerogel insulated absorber.

FIG. 18 shows a plot of an on-sun experimental run comparing thestagnation temperature (the maximum possible temperature achievable forthe given configuration and input conditions, i.e., temperature when noheat is taken away by the heat transfer fluid) of the two absorbers, onehaving an aerogel layer and one without. In operation, when heat isextracted by the HTF to generate exergy, by definition the absorbertemperature is less than the stagnation temperature. The solar flux atthe focal plane may be monitored using a circular foil radiometer“fluxgage”. The data of FIG. 18 demonstrates that at a moderateconcentration ratio of around 12 suns, the aerogel allows absorbertemperatures as high as 480° C. In comparison, the bare absorber reacheda peak temperature of 350° C.

Thus, particular embodiments of the subject matter have been described.Other embodiments are within the scope of the following claims. In somecases, the actions recited in the claims can be performed in a differentorder and still achieve desirable results. In addition, the processesdepicted in the accompanying figures do not necessarily require theparticular order shown, or sequential order, to achieve desirableresults. In certain implementations, multitasking and parallelprocessing may be advantageous.

1. An aerogel material comprising: silica aerogel defining a porous material with pores having a mean radius of less than 5 nm with a standard deviation of 3 nm.
 2. The aerogel material of claim 1, wherein the aerogel material comprises percent solids of less than 10%.
 3. The aerogel material of claim 1, wherein the aerogel material comprises a mean particle size of 1.3 nm.
 4. The aerogel material of claim 1, wherein the silica aerogel has a solar absorptance of >0.9 and IR emittance of <0.3 at a temperature of 400° C. when in thermal contact with a black absorber. 5.-36. (canceled) 